Article
Chemistry, Physical
Vidmantas Bieliunas, Sigitas Stoncius
Summary: The design and synthesis of second generation C-2-symmetric ligands with additional substituents was reported. These substituents provide a further element for fine-tuning the ligand structure by enforcing conformational rigidity. The tetrasubstituted bicyclo[3.3.1]nona-2,6-dienes were successfully employed in the rhodium-catalyzed arylation reaction with good to excellent yields and enantioselectivities up to 99% ee.
Article
Chemistry, Organic
Jessica Wahlers, Michael Maloney, Farbod Salahi, Anthony R. Rosales, Paul Helquist, Per-Ola Norrby, Olaf Wiest
Summary: This study developed and applied a TSFF method to predict the stereoselectivity of aryl boronic acids conjugate addition to enones, achieving good results through automated screening and validation. Detailed error analysis and identification of structural origins for outliers were conducted. The results showed that the majority of virtual screening outcomes were in line with expectations.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Biochemistry & Molecular Biology
Maxim M. Perfilov, Elvira R. Zaitseva, Nadezhda S. Baleeva, Vadim S. Kublitski, Alexander Yu. Smirnov, Yulia A. Bogdanova, Svetlana A. Krasnova, Ivan N. Myasnyanko, Alexander S. Mishin, Mikhail S. Baranov
Summary: In this work, we demonstrated that the addition of a trifluoromethyl group to the meta-position of arylidene imidazolones (GFP chromophore core) significantly enhances their fluorescence intensity in nonpolar and aprotic solvents. The solvent-dependent modulation of fluorescence intensity allows these compounds to be used as fluorescent polarity sensors. Specifically, we identified a compound suitable for selective labeling of the endoplasmic reticulum in living cells.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Physical
Emma K. Edelstein, Danica A. Rankic, Caroline C. Dudley, Spencer E. McMinn, Donovon A. Adpressa
Summary: A highly efficient Rh-catalyzed conjugate addition reaction for the synthesis of proline analogues was reported. The method exhibited high yield and high levels of diastereo- and enantioselectivity for the desired products. This approach was used to synthesize a variety of 3-substituted proline derivatives from readily available dehydroproline electrophiles and boronic acid nucleophiles.
Article
Chemistry, Multidisciplinary
Greta Vastakaite, Claudio E. Grunenfelder, Helma Wennemers
Summary: This study presents a tripeptide catalyst for the efficient and stereoselective synthesis of chiral succinimides via conjugate addition reactions between aldehydes and C-substituted maleimides. The catalyst exhibits high chemoselectivity and allows direct derivatization of the succinimides to access other chiral compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Xiaoxue Wu, Yanhao Su, Guofu Zi, Weiping Ye, Guohua Hou
Summary: The asymmetric hydrogenation of a-substituted alkenyl sulfones using Rh-(R,R)-f-spiroPhos complex catalyst has been successfully achieved, resulting in high yields (96-99%) of chiral ?-keto sulfones and simple a-alkyl-substituted sulfones with excellent chemo-/enantioselectivities (86-96% ee) and high turnover numbers (TONs) of up to 4000. This method provides an efficient and high-enantioselectivity strategy for the synthesis of chiral ?-keto sulfones and simple a-substituted sulfones under mild conditions. Additionally, the obtained hydrogenation product can be transformed into other important chiral a-substituted sulfones.
Article
Chemistry, Organic
Masafumi Tamura
Summary: A method for Pd-catalyzed asymmetric conjugate addition of ortho-substituted arylboronic acids to cyclic enones has been developed, which resulted in the formation of cyclic ketone products with ortho-substituted benzylic all-carbon quaternary centers in good yields and high enantioselectivity.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Seanghai Hor, Kin-ichi Oyama, Nobuaki Koga, Masaki Tsukamoto
Summary: Through investigating Bronsted acids as catalysts, trifluoromethanesulfonic acid was found to exhibit high catalytic activity in low-polar solvents for the 1,4-addition reactions, enabling the synthesis of succinimides. Furthermore, a catalytic amount of trifluoromethanesulfonic acid in toluene could also realize the 1,4-addition reactions of 1,3,5-trimethoxybenzene to acrylates.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Tongyu Bi, Yi Xu, Xin Xu, Bixi Tang, Qing Yang, Yi Zang, Zhenyang Lin, Jia Li, Weibo Yang
Summary: A Rh(III)-catalyzed C-H alkylation macrocyclization was developed to access CF3-substituted macrolides with novel bioactivities. The chemoselectivity between C-H alkylation and olefination macrocyclization was controllable, and the CF3-substituted macrolides exhibited potent anti-inflammation activities against TNF-alpha, IL-6 and CCL2 mRNA expression.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Organic
Po-Kai Peng, Jeremy A. May
Summary: A chiral 6-substituted cyclohexenone was synthesized with high yields and enantioselectivities through a bisperfluorotoluyl-BINOL catalyzed conjugate addition of trifluoroborate salts to doubly vinylogous esters and aldol condensation. Stepwise and single-pot sequences were developed, with the former also providing beta-substituted masked ketoaldehydes containing a vinyl ether. This transformation was used in a four-step total synthesis of penienone with a significantly reduced number of steps compared to previous syntheses.
Article
Chemistry, Organic
En-Ze Yao, Guo-Li Chai, Ping Zhang, Bo Zhu, Junbiao Chang
Summary: We report the enantioselective conjugate addition of organic boronic acids to beta-enaminones catalyzed by (S)-2,15-Cl-2-DHTP, providing high yields and moderate to excellent enantioselectivities (up to 98% ee). This catalytic system exhibits unique features including mild reaction conditions, high efficiency, broad substrate scope, and applicability to alkenylboronic acids and heteroarylboronic acids.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Wenwei Li, Honggui Zhou, Yequan He, Ge Zeng, Yumeng Zheng, Yangni Hu, Zhongyan Chen, Jing-Yuan Ge, Ningning Lv, Jiuxi Chen
Summary: We report a novel pathway to synthesize gamma-lactams using acetonitrile analogues as coupling partners. This method does not require oxidants, ligands, and Lewis acids, and exhibits a broad substrate scope, good functional group tolerance, and excellent chemo/stereoselectivity. Scale-up reactions and late-stage derivatizations demonstrate the potential synthetic utility of this methodology.
Article
Chemistry, Organic
Tetsuya Sengoku, Takuto Kajihara, Mari Inaba, Hidemi Yoda
Summary: A new application of amido-functionalized allylboronates in water for asymmetric 1,4-addition was developed. By using N-mesityl maleimide as a substrate and CuSO4/bis(oxazoline) catalyst, extremely high enantioselectivity (>99% ee) was achieved.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Bin Mao, Zhi-Wei Chen, Jian-Fei Wang, Chao-Huan Zhang, Zhi-Qian Du, Chuan-Ming Yu
Summary: In this study, the enantioselective organocatalytic conjugate alkenylation of fi-substituted alkenyl benzimidazoles was achieved, leading to the formation of beta-stereogenic 2-alkyl benzimidazole derivatives with excellent enantio-selectivities. Chiral binaphthols were found to be effective catalysts for promoting the nucleophilic addition of bench-stable alkenyl trifluoroborate salts under mild conditions. By utilizing C=N-containing azaarenes as activating groups, the applications of these catalysts were expanded. The synthetic utility of this strategy was demonstrated by converting the products into several useful enantiomerically enriched benzimidazole building blocks.
Article
Chemistry, Physical
Viktoria Kozma, Zsolt Szakonyi, Gyorgy Szollosi
Summary: This study reveals the structural effects of beta-amino acids on the asymmetric Michael additions, including the impact of substituent bulkiness on selectivity, the beneficial arrangement of functional groups in cis isomers, and the influence of nitrogen substituents on reaction rate and enantioselectivity.
Review
Chemistry, Multidisciplinary
Chandrasekar Praveen, Aurelien Dupeux, Veronique Michelet
Summary: The review discusses the catalytic activity of gold in functionalizing various C-H bonds with high selectivity, highlighting factors such as steric/electronic properties of C-H bonds, oxidation state of gold, and stereoelectronic capacity of coordinated ligands. It also reveals the potential applications of Au(I) and Au(III) species in regio- and site-selective activation of challenging C-H bonds, as well as the selective C-H bond activation with different heterocycles described in recent literature.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Vincent Davenel, Chloe Puteaux, Christian Nisole, Fabien Fontaine-Vive, Jean-Marie Fourquez, Veronique Michelet
Summary: Efficient routes to access functionalized bicyclo[3.2.1]oct-2-ene and bicyclo[3.3.1]nonadiene via indium-mediated cycloisomerization of 1,6-enynes have been developed. The optimization of an atom-economical catalytic process using InCl3 led to high yields of up to 99% for the preparation of functionalized bicyclic adducts. The choice between 5-exo and 6-endo pathways in the cyclization reaction was influenced by the substitution of the alkynyl moiety, with electron-withdrawing groups favoring the exo isomer.
Article
Chemistry, Inorganic & Nuclear
Idir Benaissa, Katarzyna Gajda, Laure Vendier, Noel Lugan, Anna Kajetanowicz, Karol Grela, Veronique Michelet, Vincent Cesar, Stephanie Bastin
Summary: The coordination chemistry of anionic NHC based on an IPy platform substituted at the CS position was studied with transition-metal centers, showing different coordination modes and reaction mechanisms. A gold(I) intermediate was also discovered during the process and structurally characterized. These complexes exhibited high activities and a large tolerance towards functional groups in the synthesis of carboxylic acid derivatives.
Article
Chemistry, Organic
Romain Laher, Emilie Gentilini, Christophe Marin, Veronique Michelet
Summary: The study focuses on the synthesis of original structures with bicyclic scaffolds for the fragrance industry and evaluates their potential organoleptic properties. NHC-gold-type catalysts show excellent activities in the synthesis of various bicyclic adducts. The research also compares the similarities and differences between starting ethers and their cycloisomerized bicyclic counterparts.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Vincenzo Marsicano, Antonio Arcadi, Veronique Michelet
Summary: In this study, alkyl- and aryl-substituted N-propargyl phthalimides were used as starting materials to selectively synthesize α-fluoro, β-phthalimido ketones, α,alpha-difluoro, β-phthalimido ketones, or β-phthalimido α-diketones through gold-catalyzed oxyfluorination/oxydifluorination or dioxygenation reactions. Key factors controlling product selectivity were identified, and the simultaneous assembly of the quinoxaline nucleus and removal of the phthalimido-protecting group were tested. Hypothetical reaction mechanisms for different reaction pathways were proposed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Elodie Louisy, Sandra Olivero, Veronique Michelet, Alice Mija
Summary: This study explores the potential of (R)-(+)-limonene, a major byproduct of the citrus industry, as a biobased thermoset precursor. The findings show that cis-LDO can be used to create highly promising biobased epoxy monomers for the production of high-performance thermoset materials.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Review
Chemistry, Organic
Aurelien Dupeux, Veronique Michelet
Summary: This article provides an overview of enantioselective strategies for the synthesis of oxazinoindoles and evaluates the bioactive properties of chiral oxazinoindoles.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Multidisciplinary
Elodie Louisy, Veronika Khodyrieva, Sandra Olivero, Veronique Michelet, Alice Mija
Summary: This paper presents a review of the applications of limonene oxide and dioxide as renewable raw materials for the development of biobased polymers. The polymerization techniques for limonene oxide and dioxide monomers are discussed.
Review
Chemistry, Multidisciplinary
Philippe Martinaux, Romain Laher, Christophe Marin, Veronique Michelet
Summary: This article introduces the application of transition metal-catalyzed cyclization reactions in fragrance synthesis, particularly in the synthesis of key skeletons. These reactions can improve atom economy and synthetic efficiency, providing new alternatives for the fragrance industry.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Review
Biochemistry & Molecular Biology
Romain Melot, Veronique Michelet
Summary: Coinage metals have shown great catalytic activity in organic transformation processes, making them the preferred choice for researchers. This review focuses on the recent development of coinage metal-catalyzed domino reactions using ortho-alkynylaryl and heteroaryl aldehydes and ketones, leading to functionalized heterocycles. The use of gold and silver chiral complexes as catalysts, as well as the preparation methods for chromenes and indoles, are discussed. The review also highlights the applications of copper and ruthenium in cyclization and asymmetric hydrogenation processes.
Article
Chemistry, Multidisciplinary
Kristina Plevova, Laura Juliana Prieto Pabon, Marc Gaysinski, Sophie Poulain-Martini, Veronique Michelet
Summary: Chiral Ag-atropisomeric ligand species were examined in solution at varying temperatures using P-31-NMR spectroscopy. The analysis of key parameters in Ag-BINAP complexes was conducted to understand their significance in an enantioselective transformation. An efficient silver-catalyzed intramolecular [4+2] cycloaddition of amide-1,6-enyne furnished an enantiomerically enriched tricyclic compound under mild reaction conditions using simple reagents.
Article
Chemistry, Applied
Romain Melot, Sandra Olivero, Veronique Michelet
Summary: A synthetic route for alkynylated saturated N-heterocycles was developed via a sequential combination of Shono oxidation and gold(I)-catalyzed alkynylation reaction. The electrochemical Shono oxidation enabled efficient access to various N,O-acetals through direct C-H bond functionalization of cyclic amines. The gold-catalyzed process allowed the introduction of aryl acetylene partners with different electron properties. Promising initial results on asymmetric version were obtained.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Alexis Truchon, Aurelien Dupeux, Sandra Olivero, Veronique Michelet
Summary: A gold-catalyzed orthogonal tandem reaction using HFIP as a Lewis acid has been developed to access carbocyclic ketone on naphthalene substrates. The yield of cyclic ketones ranged from 15% to 91% using a variety of acenaphthylene carbaldehydes. The mechanism involved a cyclization process followed by an [Au]-HFIP interaction for the final rearrangement. The gram-scale transformation and post-functionalization bromination were successfully carried out.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Alice Mija, Elodie Louisy, Sara Lachegur, Veronika Khodyrieva, Philippe Martinaux, Sandra Olivero, Veronique Michelet
Summary: This study valorizes the benign epoxidation of (R)-(+)-limonene to generate novel bio-resourced limonene dioxide monomers. The racemic limonene dioxide was cured with glutaric and dimethylglutaric anhydrides leading to thermosets with a high T-g and good mechanical properties.
Article
Chemistry, Organic
Maxime De Abreu, Yue Tang, Etienne Brachet, Mohamed Selkti, Veronique Michelet, Philippe Belmont
Summary: An efficient silver-catalyzed tandem reaction has been developed for the formation of 1,2-dihydroisoquinoline derivatives, providing a straightforward method to access highly functionalized multiheterocyclic scaffolds. This methodology offers a promising route for the synthesis and development of biologically relevant new heterocyclic pharmacophores, and allows for modifications at various sites of this pharmacophore.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)